Antisoil coating-containing shaped articles

ABSTRACT

Polymeric alcohol derivatives consisting of polymeric alcohol sulfonic acids containing S-xanthogenate ester substituents of the general formula AND SALTS OF SAID POLYMERIC ALCOHOL SULFONIC ACIDS PREPARED BY REACTION OF A SULTONE, E.G., 1,3-PROPANE SULTONE, WITH THE FREE ACID FORM OR A SALT OF A POLYMERIC ALCOHOL XANTHOGENATE ESTER, E.G., CELLULOSE XANTHATE. The novel omegasulfonated polymeric alcohol derivatives have physical and chemical properties, e.g., solubility, viscosity, reactivity with cross-linking agents, and an anionic character, adapting them for advantageous use in a wide range of applications. The derivatives find particular utility as antistatic and antisoiling agents which are effective when applied to a wide range of soil receptive substrates, e.g., natural and synthetic textiles.

waited States Patent Bridgeford et al.

ANTISOIL COATING-CONTAINING SHAPED ARTICLES Inventors: Douglas J.Bridgeford, Champaign; Albin F. Turbak; Noel 1. Burke, both of Danville,all of ill.

Assignee: Tee-Pak, Inc., Chicago, 111. Filed: Sept. 10, 1969 Appl. No.:856,798

References Cited UNITED STATES PATENTS 10/1968 De Paolo et a1. ..117/1395 8/1969 Schaefer et al. ..117/139.5 X

Primary Examiner-William D. Martin Assistant Examiner-Theodore G. DavisAttomey-Neal J. Mosely and David V. Munnis 5] Mar. 14, 1972 and salts ofsaid polymeric alcohol sulfonic acids prepared by reaction of a sultone,e.g., l,3propane sultone, with the free acid form or a salt of apolymeric alcohol xanthogenate ester, e.g., cellulose xanthate. Thenovel omega-sulfonated polymeric alcohol derivatives have physical andchemical properties, e.g., solubility, viscosity, reactivity withcrosslinking agents, and an anionic character, adapting them foradvantageous use in a wide range of applications. The derivatives findparticular utility as anti-static and antisoiling agents which areeffective when applied to a wide range of soil receptive substrates,e.g., natural and synthetic textiles.

37 Claims, No Drawings 'ANTISOIL COATING-CONTAINING SHAPED ARTICLES Thisinvention relates to novel sulfonated derivatives of polymeric alcoholsand, more particularly, to S-xanthogenate esters which are the reactionproducts of sultones with the free acids and salts of polymeric alcoholxanthogenate esters. The invention further relates to the use of suchpolymeric alcohol sulfonic acids and sulfonates to provide antistaticand soil repellent coatings on soil receptive substrates.

BACKGROUND OF THE INVENTION Sultones are cyclic esters ofhydroxysulfonic acids. Such compounds are recognized in the prior art tobe reactive with compounds containing nucleophilic functional groups tointroduce a sulfonic acid moiety. The versatility of the reactivity ofsultones has led to their use in the production of compounds havingwidely varied physical and chemical properties. Reactions of sultoneswith alcohols, thiols, phenols, amines, amides, mercaptans, carboxylicacids, thio acids, and phosphorous-containing compounds, for example,have been known to produce derivatives useful as detergents, wettingagents, suspending agents, bactericides, fungicides, and sizing agents.However, while the versatility of sultones has led to the preparation ofinteresting derivatives in the laboratory, the relatively high cost ofsultones in comparison with alternative sulfonation agents generally haslimited their commercial use.

The problems stemming from the surface soiling of shaped articles arewell recognized. In fabrics used for wearing apparel and other textileproducts, such as carpeting and upholstery, surface soiling not only isunattractive and usually shortens the life of the fabric but oftenpresents difficulties to proper hygiene maintenance.

To combat soiling problems, numerous approaches have been suggested inthe prior art. In general, attempts to render substrates soil repellentand/or soil releasable have involved an impregnation or coating of thesubstrate with a compound having itself some degree of one or both ofthese properties. Additives and coating agents which have been suggestedin the main are polymeric compounds which range from stronglyhydrophobic materials such as fluorinated polymers to more hydrophilicpolymers containing carboxylic, phosphoric, and/or sulfonic acidfunctionality. Compounds previously suggested, while successful inproviding protection to various substrates against certain types ofsoiling, generally have not been totally satisfactory in imparting soilresistance to even specific substrates against widely varying types ofsoil contaminants. In other instances, where impregnating or coatingagents provide 'resistance against soiling by relatively widely varyingtypes of soiling agents, the additives may still be of limited utilitydue to an inability to resist removal from the substrate when thesubstrate is subjected to the mechanical (e.g., scuffing) or chemical(e.g,, washing) operations it normally incurs. The permanence of anantisoilant on a substrate can be improved, in some instances, bychemically bonding the antisoiling agent directly or throughcross-linking agents to the substrate. This approach, however, also hashad its drawbacks mainly due to the chemical bonding interfering with ordestroying other desired characteristics of the substrate itself orother additives, e.g., permanent press additives on fabrics.

Accordingly, a search has continued in the art for altemative agentscapable of imparting improved antistatic, soil repellent and/or soilrelease properties to shaped materials, such as textiles and the like.

OBJECTS OF THE INVENTION The primary object of the present invention isto provide a novel class of sulfonated polymeric alcohol derivatives.

Another object of the present invention is to provide sulfonatedpolymeric alcohol derivatives which are easily prepared from availablestarting materials and which have valuable properties.

An additional object of the present invention is to provide novelsulfonated polymeric alcohol derivatives which are stable and watersoluble.

A further object of the present invention is to provide sulfonatedpolymeric alcohol derivatives which are stable and are soluble in waterto form aqueous solutions relatively insensitive to metal ions andorganic solvents.

Still another object of the present invention is to provide sulfonatedpolymeric alcohol derivatives which form relatively viscous, stable,aqueous solutions.

Yet a further object of the present invention is to provide sulfonatedpolymeric alcohol derivatives which easily can be applied to or formedin situ on substrates to impart antistatic, soil repellent, and/or soilreleasability thereto.

Another object of the present invention is to provide sulfonatedpolymeric alcohol derivatives which can be used alone or in combinationwith cross-linking agents to produce antistatic, soil repellent, and/orsoil releasable coatings on soil receptive substrate surfaces.

An additional object of the present invention is to provide sulfonatedpolymeric alcohol derivatives which can be applied to soil receptivesubstrate surfaces to impart antistatic, soil repellent, and/or soilrelease properties affective against a wide range of soilants.

A further object of the present invention is to provide sulfonatedpolymeric alcohol derivatives which can be used to impart antistatic,soil repellent, and/or soil release properties to a wide range of soilreceptive substrates.

Particular objects of the present invention are to provide sulfonatedderivatives of polymeric alcohols, such as cellulose and starch, havingas features the properties set forth in the aforementioned objects.

Other particular objects of the present invention are to provide treatedshaped articles, such as natural and synthetic textile articles, towhich improved antistatic, soil repellent and/or soil release propertieshave been imparted.

DETAILED DESCRIPTION OF THE INVENTION It has been found that theproperties described in the aforementioned objects are characteristicsof a novel class of compounds consisting of polymeric alcoholderivatives selected from the group consisting of (a) polymeric alcoholsulfonic acids containing S-xanthogenate ester substituents of thegeneral formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon I radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids.

The polymeric alcohol sulfonates of the present invention includewater-soluble and water-insoluble embodiments. The sulfonatedderivatives of the invention further embrace both straightS-xanthogenate esters of polymeric alcohols, mixed esters of polymericalcohols which contain, in addition to S- xanthogenate estersubstituents of the above type, unesterified xanthogenate estersubstituents and/or mixed ester ethers containing, in addition to suchester substituents, alkyl sulfonate ether substituents containingalkylene radicals -R of the type described above.

Typically, the polymeric alcohol sulfonates of the present inventionhave a degree of substitution (D.S.) with regard to all (i.e., includingboth sulfonic acidand sulfonate salt-terminated) S-xanthogenate estersubstituents in the range of from about 0.001 to about 1.0, and moreusually in the range of from about 0.01 to about 0.5, and a molecularweight of at least about 1,000 and ranging up to about 5,000,000. Moreusually, the molecular weight is in the range of from about 2,000 toabout 500,000. Embodiments of typical sulfonated derivatives of theinvention which are mixed esters and mixed ester ethers, in addition tosuch molecular weight and S- xanthogenate ester substituent D.S.characteristics, further usually have a D.S. with regard to allunesterified xanthogenate ester substituents and a D.S. with regard toall alkyl sulfonate ether substituents each of which is less than about50 percent, more usually less than about percent, of the S-xanthogenateester substituents D.S. of the derivative. The phrase degree ofsubstitution," as used herein, is intended to refer to the ratio whichexpresses the average number of a given substituent in a polymericalcohol derivative to the total number of available hydroxyl groups per100 monomeric units in the derivative. A straight cellulose S-xanthogenate ester derivative having an average of one S- xanthogenatesulfonic acid ester substituent per 100 monomeric units, therefore, hasa degree of substitution (D.S,) with regard to S-xanthogenate estersubstituents of 0.0033. A polyvinyl alcohol derivative containing anaverage of one S-xanthogenate sulfonic acid ester substituent per 100monomeric units, on the other hand, has a D.S. of 0.01 with regard tosuch substituents.

The sulfonated polymeric alcohol derivatives of the present inventionare derived from the reaction products of sultones of the formulawherein R is as defined above, with polymeric alcohol xanthogenateesters, i.e., the acid and salt forms of the reactions products ofcarbon disulfide, carbonyl sulfide, or mixtures thereof with polymericalcohols. The sultones react with the xanthogenate ester substituents inthe starting polymeric alcohol derivatives to provide S-xanthogenateester substituents of the above-defined type.

In the preparation of the sulfonated polymeric alcohol derivatives ofthe present invention, S-xanthogenate ester substituent introduction maybe effected in one or more stages using either a polymeric alcoholxanthogenate ester which initially contains sufficient xanthogenateester substituents to produce the desired S-xanthogenate estersubstituent-containing derivative or one which requires furtherxanthogenation, intermediate a reaction of the derivative with sultones,to provide the desired degree of total available xanthogenate estermoiety.

Polymeric alcohol xanthogenate esters useful as starting materials inthe present invention, accordingly, vary widely. Polymeric alcoholxanthogenate esters are known materials and constitute a well recognizedclass of compounds. Detailed procedures for preparing such compoundsincluding free acids and various salts thereof are disclosed, forexample, in US. Pat. Nos. 3,291,789, 3,330,830, 3,336,114, and3,399,069. Carbon disulfide-derived polymeric alcohol xanthogenic acidsand salts (sometimes commonly referred to as xanthates) are relativelystable and, if conditions are properly controlled, i.e., in the absenceor substantial absence of competing nucleophiles, react rapidly andessentially quantitatively with sultones. Xanthates of polymericalcohols constitute a broad class of compounds preferred for use inpreparing sulfonated polymeric alcohol derivatives of the invention.Less preferred for use in preparing sulfonated polymeric alcoholderivatives of the invention are carbonyl sulfide-derived polymericalcohol xanthogenate esters since such compounds are relatively unstableand decompose rapidly when formed. By carrying out the synthesis thereofin the presence of a sultone, however, the carbonyl sulfide-derivedxanthogenate esters can be employed as intermediates in the preparationof relatively stable sulfonated polymeric alcohol derivatives.

Examples of specific polymeric alcohol xanthogenate ester intermediatesused in the preparation of the sulfonated polymeric alcohol derivativesof the invention include watersoluble and water-insoluble xanthogenicacids and xanthogenate salts of polysaccharides of the formula (C l-I 0,such as cellulose, starch, amylose, amylopectin, dextran, and glycogen;other natural hydrocolloidal polysaccharides such as gum arabic, gumtragacanth, carob-seed gum, agaragar, algin; glucosamine polysaccharidessuch as chitin and chitosan; hydrolyzed forms of such polysaccharidessuch as alkali cellulose and acid-hydrolyzed cellulose, starch, andchitin; and other polymeric alcohols including addition polymer such aspolyvinyl alcohol, polyvinyl alcohol/polyvinyl ester copolymers, e.g.,polyvinyl alcohol/polyvinyl acetate and polyvinyl alcohol/polyvinylpropionate, and condensation polymers such as hydroxy-methylated nylons;as well as various other modified (e.g., oxidized) or derivatized (e.g.,etherified, such as hydroxyethylated and hydroxypropylated, andesterified, such as acetylated and propylated) forms of such polymericalcohols, provided such products contain hydroxyl groups reactive withcarbon disulfide or carbonyl sulfide (e.g., contain xanthatable"hydroxyl groups).

Examples of polymeric alcohol xanthogenic acid salts used in thepreparation of sulfonated polymeric alcohol derivatives of the inventioninclude water-soluble and water-insoluble inorganic and organic salts ofthe above-specified polymeric alcohol xanthogenic acids such as theammonium, alkali metal, e.g., sodium and potassium; alkaline earthmetal, e.g., calcium, magnesium, barium, zinc and strontium; heavymetal, e.g., aluminum, cadmium, iron, copper, chromium and zirconium;amine, e. g., trimethylamine and pyridine; quaternary ammonium, e.g.,benzyltrimethyl ammonium; and imine, e.g., ethyleneimine andpolyethyleneimine salts of the aforedescribed xanthogenic acids.

Certain polymeric alcohol xanthogenate esters are especially useful inthe preparation of S-xanthogenate ester sulfonated polymeric alcoholderivatives in accordance with the present invention. As thexanthogenate ester D.S. of a polymeric alcohol increases, for example,the water solubility of it and the S-xanthogenate esters, which can beformed by it, generally increases. Where it is desired to effectreaction of the sultone with the polymeric alcohol xanthogenate ester insolution, or where the resultant S-xanthogenate ester is desired to bewater-soluble, the xanthogenate reactant preferably has a sufficientlyhigh D.S. with regard to xanthogenate ester substituents to bewater-soluble and impart water-solubility to the S-xanthogenate estersproduced. For polymeric alcohol xanthogenate esters having a molecularweight of less than about 200,000, for example, a minimum xanthogenateester D.S. in the ester reactant in the range of from about 0.005 toabout 0.15 usually is sufficient to impart adequate water-solubility andviscosity properties to the free acid, ammonium, and alkali metal saltforms of the resultant S- xanthogenate esters of corresponding D.S.produced therefrom. Soluble Sxanthogenate esters produced in accordancewith the present invention, and in particular the cellulosexanthate-S-alkane sulfonates, produce solutions which are considerablymore viscous than the xanthogenate ethers of comparable D.S. from whichthey are prepared. Indeed, a feature of the present invention is thatthe xanthogenate esters of the present invention display viscositieswhich attain surprisingly high levels in comparison to viscositiescharacteristic of other polymers, including sulfonated polymers, ofequivalent molecular weight and functionality. An S-xanthogenate ester,accordingly, while soluble, normally may vary from a gel in water, forexample, and form pourable solutions only at undesirable lowconcentration, e.g., below 0.5 percent. In instances where solubleS-xanthogenate esters are desired, the D.S. of the xanthogenate etherreactant employed in the preparation thereof may also be preferred to besufficiently high to produce sulfonated derivatives which are capable offorming solutions of minimum concentrations, eg. about 2 percent.

The molecular weight of the starting polymeric alcohol xanthogenateesters is also important to the production of preferred S-xanthogenateesters of the invention. At lower molecular weights, e.g., those belowabout 25,000, polymeric alcohol xanthogenate esters produce the moresoluble S- xanthogenate ester derivatives. The more preferred sulfonatedderivatives of the present invention are produced using polymericalcohol xanthogenate esters of a sufficiently high molecular weight,e.g., above about 50,000, to render the ultimate Shxanthogenate estersfilm-forming. Particular examples of such preferred film-formingsulfonates are the water-soluble S-xanthogenate esters derived fromcellulose xanthates having a degree of polymerization (DR) of at leastabout 100 and in the range from about 150 to about 550. Film-formingsulfonate derivatives formed from polymeric alcohol xanthogenate estersof the higher molecular weights, e.g., cellulose xanthates of molecularweight above about 100,000 and xanthates of the hydrocolloidalpolysaccharides, such as dextran, of molecular weights above about300,000 are less soluble. Accordingly, the sulfonated derivativesproduced from such higher molecular weight polymeric alcoholsxanthogenates may not produce solutions which, for example, are easilycoatable on substrates. Highly useful S- xanthogenate ester derivatives,on the other hand, can be produced from such high molecular weightxanthogenate esters in situ on substrates upon which coatings of thesulfonate derivatives are desired.

As described in U.S. Pat. Nos. 3,291,789, 3,330,820, 3,336,114, and3,399,069, the conventional technique for preparing polymeric alcoholxanthogenates involves a reaction of a polymeric alcohol with carbondisulfide, carbonyl sulfide, or a mixture thereof at a pH in excess of13 and produces resultant xanthogenates containing significant amountsof excess caustic and byproduct sulfur compounds including thio-,dithio-, and trithiocarbonic acid salts. Alkalis and thio acids, such asthose present as contaminants in conventionally prepared polymericalcohol xanthogenates, are reactive with sultone. The preferredpolymeric alcohol xanthogenates for use in preparing sulfonatedderivatives of the invention, accordingly, are those which have been atleast decausticized to a pH below about 13 and more preferably belowabout 12. The more preferred polymeric alcohol xanthogenates are those,which in addition to being decausticized, are substantially free ofxanthogenation sulfur byproducts. Decausticizing of such materials maybe carried out by treatment with weak acids, solvent extraction, or asdescribed in U.S. Pat. No. 3,29l,789, by treatment of solutions orsuspensions of crude polymeric alcohol xanthogenates with cationexchangers, anion exchangers, combinations of cation and anionexchangers, ion retardation resins, and membranes such as dialysismembranes which are permselective with regard to the caustic. Certain ofsuch treatments, i.e., the use of anion exchangers, ion retardationresins, and permselective membranes are also effective to remove sulfurbyproducts. Alternatively, removal of xanthogenation byproduct sulfurcontaminants may be effected, as shown in U.S. Pat. No. 3,399,069, byspray drying a previously decausticized polymeric alcohol xanthogenate.

Specific examples of sultones suitable for use in the preparation of thesulfonated polymeric alcohol derivatives of the present inventioninclude l,3-propane sultone, 1,4-butane sultone, l,5-pentane sultone,and the lower alkyl substituted derivatives thereof such as2,2-dimethyl-l,3-propane sultone, 2,2-diethyl-l,3-propane sultone,2,2-dipropyl1,3-propane sultone, 2,3-dimethyl-l,3-propane sultone,l,2,3-trimethyl-l,3- propane sultone, 2,2-dimethyl-l,4-butane sultone,and mixtures of isomeric butane sultones (prepared from mixtures ofchlorobutane sulfonic acids which are obtained by sulfochlorination ofl-chlorobutane). The preferred sultones are the gamma-sultones and, moreparticularly, 1,3-propane sultone.

In accordance with the present invention, the sultone can be reactedwith the polymeric alcohol xanthogenic acid or xanthogenic acid saltintermediate in a number of ways, the preferred technique dependingprimarily upon the nature of the polymeric alcohol xanthogenateintermediate. In general, the reaction can be carried out with thepolymeric alcohol intermediate in the form ofa'solid, a gel, or asolution or suspension in an aqueous or organic liquid medium. In anysystem utilized, the system preferably is free of compounds havinganions (other than hydroxyl ions) which compete with the xanthogenatefor the sultone.

In certain preferred embodiments, the polymeric alcohol xanthogenate isreacted with the sultone in the form of an aqueous or organic solventxanthogenate solution. Such embodiments have the advantage of proceedingrapidly. In other preferred embodiments, the polymeric alcoholxanthogenate is suspended in a suitable liquid for reaction with thesultone. Such embodiments have the advantage in allowing for ease ofrecovery of the sulfonated derivative produced. In instances whereinsuspensions of the xanthogenates are utilized, however, it may be, andoften is, desirable to incorporate into the system water or otherhydrophilic liquids which swell the polymeric alcohol xanthate to allowfor uniformity of conversion and to increase speed of reaction.

Although water is reactive with sultones, it may be used in reactionsystems employed in the present invention since the sultone-xanthogenatereaction is significantly faster than the sultone-water reaction.Indeed, the ease and efficiency with which sultones react with polymericalcohol xanthogenates to produce the sulfonated polymeric alcoholderivatives of the invention is a particularly advantageous feature ofthe invention. Relatively high hydroxyl ion concentrations, however, maygive rise to undesirable losses of the relatively expensive sultonereactant. The presence of excess amounts of caustic in water or otherionizable reaction media should be avoided. When such systems areemployed, highly acid conditions at the initiation of the reaction alsoshould be avoided to avoid regeneration of the polymeric alcohol.

In preparing the sulfonated derivatives of the present invention,sufficient total amounts of the sultone reactant is added to the systemto effect the desired degree of conversion of xanthogenate estersubstituents in the polymeric alcohol xanthogenate ester reactant toS-xanthogenate ester substituents. The addition and/or consumption ofsultone reactant in amounts corresponding to mole ratios of sultone toxanthogenate ester substituents ofless than 1:] result in mixedS-xanthogenate esters containing unesterified xanthogenate estersubstituents. In general, sultone addition and the S- xanthogenateesterification reaction is controlled to esterifying with sultone atleast 50 percent, and preferably at least percent, of the xanthogenateester substituents. More preferred S-xanthogenate esters are produced byproviding sultone to the reaction in amounts sufficient to convertessentially all xanthogenate ester substituents in the polymeric alcoholderivative reactant to S-xanthogenate ester substituents. Where thepolymeric alcohol xanthate ester reactant contains free hydroxyl groups,sultone in amounts corresponding to mole ratios of sultone toxanthogenate ester substituents in excess of 1:1 may be added and aportion of the excess consumed in a sultone-ether reaction, provided thepH is sufficiently high at some time of reaction to favor etherformation. Such reaction products are mixed S-xanthogenate esterderivatives containing alkyl sulfonate ether substituents, the latterresulting from the reaction of the sultone with hydroxyls of thepolymeric alcohol derivative. In general, such excess sultone reactionwith the polymeric alcohol xanthogenate ester intermediates iscontrolled to maintain the D.S. of alkyl sulfonate ether substituentsintroduced into the S- xanthogenate esters produced at levels which areless than about 50 percent, and more usually less than about 10 percentof the S-xanthogenate ester substituent D.S. of the derivatives.

The manner of sultone addition to the sultone-xanthogenate etherreaction may vary.

The total amount of sultone to be reacted may be added batchwise. Batchaddition of the sultone may be advantageous, for example, in instanceswherein the xanthogenate ester employed in the reaction is produced insitu by a reaction in the system of a polymeric alcohol and carbonylsulfide or a carbonyl sulfide/carbon disulfide mixture. Alternatively,sultone addition can be carried out in increments in an intermittent orcontinuous manner. Incremental addition may be preferred, for example,in instances wherein the slower reacting but competing anioncontributing compounds, such as water, are present in the reactionsystem.

The resultant polymeric alcohol S-xanthogenate esters produced by thereaction of sultones with the polymeric alcohol xanthogenate esters,depending upon the nature thereof and ultimate use contemplatedtherefor, then may be utilized as such or subjected to a furthertreatment. Further treatments contemplated for use include contactingthe S-xanthogenate ester derivative with an acid, base, salt,cation-exchanger and the like to partially or totally alter the natureof the cations thereof. The sulfonic acid forms of the S-xanthogenateesters of the invention are significantly more stable than thecorresponding salts. Where the sulfonated derivatives are produced assalts and the materials are to be stored, they preferably are convertedto the free acid form by a suitable technique, such as by contact with astrong acid cation ion exchanger in the hydrogen ion form and the like.Other treatments contemplated to be carried out on polymeric alcohol S-xanthogenate esters produced in the invention, especially in cases wherecoatings thereof are formed on substrates by deposition or in situformation, include an application of heat and/or reaction of theS-xanthogenate ester derivatives with cross-linking agents, alkalineearth or heavy metal compounds or other substances such as polymericbases, e.g., polyethylene imine, which effect insolubilization orfurther insolubilize the resultant sulfonated derivative.

The sulfonated derivatives of the present invention have valuableproperties, those particularly obtaining depending upon the givensulfonate derivative. As a general rule, the sulfonate derivatives ofthe invention have properties which enable them to impart to substratesupon which they are deposited varying degrees of antistatic, soilrepellent, and soil release properties. Embodiments that arewater-soluble form solutions which are relatively viscous, and displaystability toward salts and organic liquids. The lower molecular weightsulfonate derivatives, e.g., of a molecular weight below about i000,produce relatively easily soluble coatings which, however, do produce aprotective effect due to scaffolding. The protective effect moreover canbe improved by providing the derivatives in the form of heavy metalsalts or reacting them with cross-linking agents after deposition on thesubstrate.

The higher molecular weight polymeric alcohol sulfonate derivatives ofthe invention and, in particular, film-forming embodiments thereof,e.g., having a molecular weight above about 25,000, constituteespecially advantageous antistatic, soil repellent, and soil releaseagents. Protection provided substrates on which such sulfonatederivatives are deposited advantageously extends to a wide range of bothhydrophilic and organophilic soiling agents. Certain embodiments of suchfilm-forming sulfonated derivatives, e.g., the cellulose-S- xanthateester sulfonates, display superior soilant protection even afterrepeated attempts to remove the sulfonated derivatives by washing. Thiseffect is observed even though the cellu lose-S-xanthate estersulfonates themselves are water-soluble and the use of heavy metalsalts, cross-linking agents and other insolubilizing agents is omitted,although such insolubilizing expedients are contemplated, and indeedpreferred, for use.

The sulfonated polymeric alcohol derivatives of the invention areeffective for use in providing antistatic, soil repellent, and/or soilrelease coatings on a wide range of soil receptive substrate materials.The sulfonated polymeric alcohol derivatives of the present inventionfind effective use, for example, as coatings on hydrophilic andhydrophobic natural and synthetic substrates such as textiles (e.g.,filaments, fibers, yarns, and woven and nonwoven fabrics), films, andother shaped or molded articles formed of glass; metals, such asaluminum, copper, and iron; ceramics; cellulosic materials, such ascotton, rayon, and paper; proteinaceous materials, such as wool andsilk; polyesters, such as polyethylene glycol terephthalate, e,g.,Dacron; polyamides, such as nylons; polyurethanes; and polymers ofolefinically unsaturated compounds, such as polyacrylonitrile, e.g.,Orlon and Dacron, polyvinyl chloride, polyvinylidene chloride, polyvinylalcohol, polyvinyl acetate, polymethyl methacrylate, polyethylene,polypropylene, and polystyrene.

Deposits of the sulfonated derivatives of the invention on substratesurfaces can be effected by various ways. Usually, the desireddeposition of an S-xanthogenate ester derivative is accomplished byinitially applying to the substrate surface desired to be covered acoating of an aqueous or organic solvent solution or dispersion of theS-xanthogenate ester and subsequently treating the coated substrate toremove the solvent liquid from the coating. Application of the S-xanthogenate ester solution or dispersion in such methods may be carriedout by any available coating technique which provides suitably uniformcoatings including those utilizing a spraying of the solution ordispersion, immersion of the substrate in a bath of the solution ordispersion, or a transfer of the solution or dispersion from a baththereof to the substrate by a conventional mechanical transfer coatersuch as those having rolls, pads, and the like. Removal of the solventliquid from the resultant coated substrates may be carried out byevaporation or contacting the coated substrate with a coagulation bath.Alternatively, deposition of an S-xanthogenate ester on a substrate canbe carried out by forming the S- xanthogenate ester derivative in situon the substrate surface. In such embodiments, for example, a coating ofa polymeric alcohol xanthogenate ester initially may be applied to thesubstrate in the manner described above with regard to S- xanthogenateester derivatives. The deposited xanthogenate ester then may becontacted with a sultone to produce the desired S-xanthogenate esterderivative in situ on the substrate surface.

The amount of sulfonated derivative deposited on a substrate inparticular embodiments varies depending on the nature of the particularsulfonate derivative utilized, the substrate being treated, and thedegree and duration of protection desired or practical under thecircumstances. In the treatment of textiles according to the presentinvention, for example, the polymeric alcohol S-xanthogenate esterderivatives of the present invention typically are deposited assubstantially uniform coatings on the textiles in total amounts fallingin the range of from about 0.005 to about 5 percent by weight of thetextile.

Although coatings of the polymeric alcohol S-xanthogenate esterderivatives of the present invention produced as described above areeffective, without further treatment, to impart antistatic, soilrepellent, and soil release properties to substrates on which they areapplied, these and other properties, such as the adherence of thecoatings to the substrate, can be improved by providing, in the ultimatecoatings, one of the more highly insolubilized forms of theS-xanthogenate ester derivatives. lnsolubilized forms of theS-xanthogenate esters of the present invention can be produced by heattreating the S-xanthogenate esters at temperatures in excess of aboutC., e.g., in the range of from about C. to about C, for suitableperiods, reacting the S-xanthogenate esters with cross-linking agents,and/or, where they are not already in such form due to a previousintermediate treatment or an in situ formation thereof, converting theester derivatives to heavy metal salts. Reactants for insolubilizing theS- xanthogenate esters such as cross-linking agents and heavy metalcompounds may be incorporated into solutions or dispersions originallyapplied to the substrates and become activated and react with theS-xanthogenate esters during or subsequent drying or curing treatment.Alternatively, such insolubilizing reactants can be incorporated into abath or spray which contacts a previously deposited wet or dry S-xanthogenate ester coated substrate. That heating can be employed toprovide insolubilized deposits of the S-xanthogenate esters which retainsulfonate substituents and substantially all of the original antistatic,soil repellent, and soil release properties of the unheated coatings isa particularly valuable and important feature of the present invention.

Cross-linking agents suitable for use in insolubilizing coatings ofS-xanthogenate esters of the invention are any compounds containing twoor more functional groups reactive with hydroxyl groups and includediisocyanates, such as 1,4-

toluene diisocyanate; aldehydes such as formaldehyde andglutaraldehyde', polymethylol derivatives such as water-solubleurea-formaldehyde condensation products and trimethylol melamine; andepoxides such as butadiene diepoxide. Typical heavy metal compoundsuseful in converting S-xanthogenate esters to insolubilized form includewater-soluble inorganic and organic bases and salts such as thewater-soluble hydroxides, chlorides, nitrates, sulfates, acetates,citrates, and the like of multivalent heavy metals and transition metalssuch as aluminum, zinc, iron, chromium, and zirconium. Alkaline earthmetals are generally ineffective to insolubilize soluble esters. Indeed,a feature of the present invention is that the solutions ofS-xanthogenate esters of the invention are surprisingly tolerable to anaddition of alkaline earth metal salts.

Supplemental agents also may be combined with the S- xanthogenate esterderivatives of the present invention in providing improved coatings onsubstrates such as textiles. Such supplemental additives suitably mayinclude conventional antisoiling agents such as polyacrylic acid, sodiumpolystyrene sulfonates, extenders, e.g., film-forming polymers such ascellulose xanthates, starch xanthates, starch, and polyvinyl alcohol, aswell as conventional coating adjuvants such as pigments, dyes, opticalpromoters, and plasticizers.

In accordance with the present invention, especially valuable coatingmaterials for soil receptive substrates, and particularly for textiles,have been found to be constituted by film coatings formed from mixturesof water-soluble film-forming polyvinyl alcohols and water-solublefilm-forming S-xanthate ester cellulose derivatlves of the invention inthe form of either free sulfonic acids or alkali metal salts, e.g.,cellulose xanthate-S-propane sulfonic acids and cellulose xanthate S-propane-sodium sulfonates. Embodiments of such mixtures typicallycontain up to about 200 parts of the polyvinyl alcohol resin per 100parts of weight of the cellulose S- xanthogenate ester derivative. Withor without cross-linking or metal salt treatment, these mixtures can beapplied as water solutions to a wide range of natural and syntheticfabrics and dried to provide coatings thereon which have surprisingresistance to removal by water, aqueous detergent solutions, andconventional organic solvents and display excellent soil resistance andsoil releasability to both hydrophilic and organophilic soiling agents.

The invention having been described'in detail, the following examplesare given to illustrate specific embodiments of the polymeric alcoholS-xanthogenate esters of the present invention and uses thereof. It willbe understood that the examples are given for illustration purposes andnot by way of limitation.

EXAMPLE 1 This example illustrates a cellulose xanthate-S-propanesulfonic acid derivative of the present invention.

15.5 grams of a cellulose xanthate having a xanthate ester substituentD.S. of about 0.16 (xanthate sulfur content of about 19.6 percent, drycellulose basis) and a D.P. of about 200 and prepared by spraydrying aviscose of comparable D.P. decausticized to a pH of about 9.0 with astrong acid cation-exchange resin in the hydrogen ion form (Dowex 50-H)is dissolved in 1421 grams of water at 4 C. To the resultant solutionare added about 3.8 grams of propane sultone. The resultant mixture isallowed to react for about 2.5 hours. At the end of this period, thetemperature of the reaction medium has risen to about 16 C. Thissolution is then allowed to further react overnight in a refrigerator.An analysis carried out on the resultant product produced indicates theproduct contains about 0.5 percent xanthate sulfur or that about 97percent of the xanthate substituents in the cellulose xanthate reactanthave been converted to xanthate-S-propane-sulfonate substituents.Quantitative conversion of the sultone reacted to S-propane-sulfonatederivatives is verified by contacting one half of the product solutionuntil equilibrium is reached with first an anion exchange resin in thehydroxyl ion form (Amberlite 1RH-400) and then a cation exchange resinin the hydrogen ion form (Dowex 50H) and titrating the ionexchangedmaterial with sodium hydroxide.

The other half of the product solution produced is diluted with about600 ml. of water, then acidified with 10 percent hydrochloric acid, andthen sodium chloride is added to saltout the sulfonated product. Theresultant precipitate is filtered, washed with methanol, refiltered, andthen dried under vacuum. The resultant product is a nearly white powderwhich redissolves easily in water at 2 percent concentration to yieldsolutions having a pH of about 3. Tests carried out at intervals onsamples of the powdery product and the solutions formed thereby revealthe materials are essentially stable over periods of several months.

EXAMPLE 2 This example illustrates another embodiment of the cellulosexanthate S-propane sulfonate derivatives of the invention.

About 20 grams of a cellulose xanthate having a xanthate ester D.S. ofabout 0.06 (xanthate sulfur content of about 8.4 percent, dry cellulosebasis) and a D.P. of about 415 obtained by spray drying a viscose ofcomparable D.P. decausticized to a pH of about 10 with a strong acidcation-exchange resin in the hydrogen ion form (Dowex 50-H) is dissolvedin 500 ml. of water at about room temperature, about 4.5 grams ofpropane sultone are added, and the reaction is allowed to proceed. Inabout three minutes, the solution gels. At the end of two hours totalreaction time, a resultant gel of cellulose xanthate-S-propane sulfonateis formed and can be diluted with water to give l percent clear,gel-free solutions. Analysis reveals substantially complete conversionof xanthate substituents to xanthate-S-propane sulfonate substituents.

EXAMPLES 3-5 These examples illustrate additional embodiments of thecellulose xanthate-S-propane sulfonate derivatives of the invention.

20 grams of three cellulose xanthate products having a D.P. of about 515and xanthate ester substituent degrees of substitution of about 0.04,0.09, and 0.13, respectively, and obtained by spray drying viscosesdecausticized to a pH of 9-10 are dissolved separately in 1,000 ml. ofwater and to the respective solutions, 3 grams, 6 grams, and 8 grams ofpropane sultone are added. The mixtures are allowed to react at roomtemperature for two hours, after which time conversion of xanthate estersubstituents in the derivatives to xanthate-S- propane sulfonatesubstituents is essentially complete and all reaction mixtures are inthe form of gels. The gels are then diluted to samples of either 0.5percent or 1.0 percent concentration and the Brookfield viscosities ofthe resultant mixtures are measured at 24-26 C. The results of themeasurements are shown in Table 1 below.

This example illustrates a further embodiment of the cellulosexanthate-S-propane sulfonate derivatives of the invention.

About 4 parts of cellulose xanthate product having a xanthate estersubstituent D.S. of about 0.20 (xanthate sulfur content of about 25%,dry cellulose basis) and a D.P. of about 375 and obtained by spraydrying a viscose decausticized to a pH of about 9.5 is dissolved inparts water and to the resultant solution about 1.8 parts of propanesultone are added. The resultant mixture is held at 13 C. with stirringfor 1.5 hours and then is heated to 22 C., at which temperature thesystem gels after 15 minutes. The mixture is allowed to further reactfor four hours at room temperature and then is stored overnight at 4 C.Analysis reveals the xanthate substituents of the resultant cellulosederivative essentially all are in the form of xanthate-S-propanesulfonate substituents. The solid sulfonic acid form of the derivativeis recovered by acidifying the gel product with percent sulfuric acid,adding eight parts sodium chloride to the acidified system, and thenfiltering, methanol washing, and drying the resulting precipitate.

EXAMPLE 7 This example illustrates a starch xanthate-S-propane sulfonatederivative of the invention.

About 70 grams of a starch xanthate product having a xanthate estersubstituent D.S. of about 0.4 (xanthate sulfur content of about 5.7percent, dry starch basis) and obtained by spray-drying an aceticacid-neutralized pearl starch xanthate are dissolved in 1,000 ml. ofwater at 25 C. About 7.2 grams of propane sultone are added over aperiod of 1.25 hours to the solution and allowed to react with thestarch xanthate. At the end of this period, a readily pourable productsolution is obtained in which analysis reveals, substantially alloriginal xanthate ester substituents of the starch derivative areconverted to xanthate-S-propane sulfonate substituents.

EXAMPLE 8 This example illustrates an embodiment of an amylosexanthate-S-propane sulfonate derivative of the invention.

About 20 grams of an amylose xanthate product having a xanthate estersubstituent D.S. of about 0.07 and a D.P. of about 500 and prepared inaccordance with the procedure of Example 3 of U.S. Pat. No. 3,399,069 byspray-drying starch xanthate decausticized by dialysis is dissolved in500 ml. of water and 6 grams of propane sultone are added to thesolution, the mixture is allowed to react at 25 C. for 2 hours. Theresultant product is an amylose xanthate derivative having axanthate-S-propane sulfonate substituent D.S. comparable to the xanthateester D.S. of the starting amylose reactant.

EXAMPLE 9 This example illustrates an embodiment of a polyvinyl alcoholxanthate-S-propane sulfonate derivative of the invention.

About 20 grams of a polyvinyl alcohol xanthate product having a xanthateester D.S. of about 0.3 and a D.P. of about 1,000 and produced inaccordance with the procedure of Example 4 of U.S. Pat. No. 3,399,069 byspray-drying polyvinyl alcohol xanthate decausticized by dialysis aredissolved in 500 mlQof water. 10 grams of propane sultone are then addedand the resultant mixture allowed to react at 25 C. for 2 hours.Analysis of the product which is recoverable from the resultant solutionusing the acidification and salting-out and techniques of the aboveexamples reveals it is a polyvinyl alcohol xanthate-S-propane sulfonicacid having a D.S. of S- xanthate ester substituents comparable to thestarting polyvinyl alcohol xanthate ester derivative.

EXAMPLE 10 This example illustrates an embodiment of achitinxanthate-S-propane sulfonate.

A sample of industrial grade chitin is ground to 60 mesh and 26 grams ofthe resultant material held in 300 ml. of concentrated (50 percent)sodium hydroxide overnight in a refrigerator. The resultant mixture iscentrifuged and a slush obtained which is diluted with water andrecentrifuged. The alkali chitin centrifugate obtained is transferred toa closed bottle. About 100 grams of carbon disulfide then are added andthe resultant contents reacted at 28 C. for 2 hours while the bottle isslowly rotated. During the reaction the initially ivory colored chitinshifts to yellow-orange. About 150 ml. of water are then added and theslurry is refrigerated at about 05 C. for 2 days. The resultant solutionobtained is diluted to 1,000 ml. to provide a solution containing about2.6 percent chitin. About 550 ml. of the solution is diluted with lliter of water, and, with blending, glacial acetic acid is added tobring the pH to 6. The combination of the blending and acidificationeffects a removal of a major portion of the byproducts originallypresent. After sodium hydroxide pellets are added to a sodium hydroxideconcentration in the chitin xanthate solution of 3 percent, about 11grams of propane sultone dispersed in 300 ml. of water are added. Theresultant mixture is allowed to react at about 36 C. for about 16 hours.About 400 ml. of the resultant product solution then are combined with amixture of 50 grams sodium chloride and 50 ml. aqueous 10 percenthydrochloric acid in 1000 ml. methanol. Centrifuging of the resultantmixture yielded a chitin-xanthate-S- propane sulfonic acid producthaving a S-xanthate ester D.S. of about 0.2l and a molecular weightofabout 500,000.

EXAMPLE 11 This example illustrates embodiments of the polymeric alcoholxanthate-S-propane sulfonate derivatives which are salts other thansodium salts.

A series of stainless steel columns are charged with a strong cationexchange resin (Dowex 50W X8) in the hydrogen ion form. The cationexchange resins then separately are converted to the ammonium,potassium, calcium, barium, cadmium, aluminum, trimethylamine, pyridine,and benzyltrimethylammonium salt forms by treatment with 5 percentaqueous solutions of ammonia. potassium hydroxide, calcium chloride,barium chloride, cadmium nitrate, aluminum nitrate, trimethylamine,pyridine, and benzyltrimethylammonium hydroxide, respectively. Througheach column is then passed 0.25 percent aqueous solutions of thecellulose xanthate-S- propane-sulfonic acid product produced in Example1 by treatment of the derivative with anion and cation exchange resins.

The resultant solutions obtained are stable solutions or dispersions ofthe ammonium, potassium, calcium, barium, cadmium, aluminum,trimethylamine, pyridine and benzyltrimethylammonium salts,respectively, of cellulose xanthate- S-propane sulfonic acid.

Repeating the procedure to contact in the columns each, in turn, 0.25percent aqueous solutions of starch xanthate-S- propane sulfonic acid,amylose xanthate-S-propane sulfonic acid, and polyvinyl alcoholxanthate-S-propane sulfonic acid derivatives, obtained by subjecting thestarch, amylose, and polyvinyl alcohol sulfonate derivatives of Examples7, 3, and 9, respectively, to the anion exchange resin-cation exchangeresin treatment of Example 1, results in stable solutions of similarsalts of the starch, amylose, and polyvinyl alcohol xanthate-S-propanesulfonic acids.

Films of the salt solutions are placed on glass and allowed to air dryat room temperatures. Certain of the resultant dried salts, i.e., thecadmium and aluminum salts could not be redissolved in water. Theremaining dried salts redissolved.

Example 12 This example illustrates embodiments of other cellulosexanthate-S-alkane-sulfonate derivatives of the invention.

The procedure of Example 1 is repeated except that each 1,4-butanesultone, 1,5-butane sultone, 2,2-dimethyl-l,3- propane sultone,2,2diethyl-l ,3-propane sultone, 1,2,3- trimethyl propane sultone, andisomeric mixtures of butane sultones are substituted in equimolaramounts for the 1,3- propane sultone utilized.

The resultant products produced are cellulose xanthate-S- alkanesulfonate derivatives containing an alkylene group in the sulfonateproduct corresponding to the alkylene group of the sultone reactant andhaving a D.S. with regard to xanthate- S-alkane sulfonate substituentsof about 0. l6.

EXAMPLE 13 This example illustrates the preparation of a polymericalcohol xanthate-S-alkane sulfonate derivative by reaction of a sultonewith a polymeric alcohol xanthate suspended in an organic liquidreaction medium.

About grams of a crude sodium cellulose xanthate crumb in which thecellulose has a xanthate ether substituent D.S. of about 0.16 (xanthatesulfur content of about 20 percent, dry cellulose basis) is slurried ina mixture of 500 ml. of

isopropanol, 200 ml. water, and 19 ml. of acetic acid diluted to 50 ml.with isopropanol. About 12.4 grams of propane sultone are added, and theresultant slurry mixture is allowed to react at 25 C. for about 16hours. The resultant product produced is easily soluble in water at 1percent concentrations. Analysis reveals the cellulose product has axanthate-S propane sulfonate substituent D.S. substantially the same asthe xanthate D.S. of the starting xanthate crumb.

EXAMPLE 14 This example illustrates the preparation of polymeric alcoholS-xanthogenate esters of the present invention by reacting a sultonewith polymeric alcohol xanthogenate esters formed in situ.

About 20 grams of sodium cellulose (D.P. about 250), 2 grams of carbondisulfide, 2.3 grams of propane sultone are added to a Sigma blade mixerand allowed to react at about 25 C. with mixing for 45 minutes. Theresultant product is dissolved in water at a 0.9 percent concentrationand subjected to treatment with an anion exchange resin and a cationexchange resin as in Example 1. The product thereby formed is acellulose xanthate-S-propane sulfonic acid derivative.

EXAMPLE 15 This example illustrates further embodiments of thepreparation of polymeric alcohol S-xanthogenate esters of the inventionby reacting a sultone with in situ formed polymeric alcohol xanthogenateesters.

The procedure of Example 14 is repeated for two runs except that thereaction is carried out at about C. for 6 hours, (a) in one run,carbonyl sulfide additionally is metered into the mixer at a constantrate of about 2 cubic liters per hour, and (b) in the other, carbondisulfide is omitted and carbonyl sulfide is metered into the mixer at aconstant rate of about 4 cubic liters per hour.

The resultant products are both found to be water-solublecellulose-S-xanthogenate ester derivatives.

The properties of the polymeric alcohol S-xanthogenate esters of theinvention advantageously adapt then for a wide range of uses. Thefollowing examples illustrate certain applications of the S-xanthogenatederivatives.

EXAMPLES 16 This example illustrates the use of the S-xanthogenateesters of the invention as coating agents which impart soil repellentand soil release properties to a polyester substrate.

In this example, a 1 percent aqueous solution ofa cellulosexanthate-S-propane sodium sulfonate having a D.P. of about 375 and axanthate-S-propane sulfonate substituent D.S. of about 0.20 and preparedas in Example 6 is employed. This solution is applied by immersion andpadding to 10 inchesXS inches pieces of a polyester fabric (formed ofpolyethylene glycol terephthalate fibers marketed by Eastman KodakCompany under the trademark Kodel IV) and the resultant coated fabricsare dried at 105 C. for about minutes. The resultant sulfonated polymeraddons are substantially uniform coatings on the fabrics in totalamounts corresponding to 0.5-0.7 percent by weight ofthe polyesterfabrics.

Several coated samples are tested to determine the durability of thesulfonated polymer coatings. In these tests one sample, after drying atabout 100 C., is immediately washed with water at 60 C. and the amountof sulfonate retained then is determined by conventional stainingtechniques using methylene blue. In another test, a sample of the coatedpolyester fabric is enclosed in a bottle along with water and heldtherein at 60 C. for extended periods. At intervals, a portion of thefabric is removed from the bottle and the retention of the sulfonatedcoating thereon is tested by methylene blue staining. These testsrevealed that the coating provided the dried cellulosexanthoate-S-propane sodium sulfonate is essentially totally resistant toremoval by simple washing and retains its sulfonate functionality evenafter 6 months storage in damp, humid environments.

To test the antisoiling properties of the coating produced by thesulfonated cellulose derivative, other samples of the coated fabricseparately are initially soiled with a deposit of one of crankcase oil,motor oil, French dressing, mustard, chocolate, and lipstick, washed inan aqueous solution of a household detergent, and then examined todetermine objectively the degree of success the coated fabric enjoys inrepelling the various soilants. Parallel soiling and washing tests areconducted on uncoated samples of the polyester fabrics and serve ascontrols. The soiling tests reveal that, while the control displaysessentially no resistance to stains by the soilants, the sulfonatederivative-coated polyester fabrics, even after three washings, areresistant to soiling by the motor oil, French dressing, mustard, andchocolate. The tests further show that treated fabric is soil resistantto lipstick stains through two washings and show some improvement, ascompared to the control, in regard to resisting staining by crankcaseoil.

EXAMPLE 1? Example 16 is repeated except that O.l percent of adiisocyanate cross-linking agent (diisocyanate derived from 36- carbondimerized aliphatic acids and marketed by General Mills, Inc. as DDIdiisocyanate") is added to the cellulose xanthate-S-propane sulfonatecoating solution and the drying of treated fabrics is carried out at 140C. for 10 minutes to allow the diisocyanate to cross-link sulfonatedderivatives coating.

The resultant polyester fabric produced have slightly more adherentsulfonated derivative coatings show and evidence antisoiling propertiessimilar to the treated fabrics of Example EXAMPLE 18 Example 16 isrepeated except that after application of the cellulosexanthate-S-xanthate sulfonate solution, the resultant fabric is immersedin a 5 percent aqueous solution of zirconium chloride, washed in tapwater, and then dried at about C.

The resultant zirconium sulfonate salt coating on the treated fabricshows greater durability than the coating of Example 16 but somewhatpoorer anti-soiling characteristics. the antisoiling properties of thezirconium salt treated fabrics, however, still are significantlyimproved as compared to the control.

EXAMPLE 19 Example 16 is repeated except that the cellulose xanthate-S-propane sulfonate utilized is the sulfonic acid form of the cellulosexanthate-S-propane sulfonate of Example 6, the sulfonic acid derivativebeing obtained by subjecting that sulfonate derivative to cationexchange as in Example 1.

The resultant coatings of the sulfonic acid derivative on the polyesterfabrics are found to give improved antisoil properties to the fabricscompared to those of the coatings of the treated fabrics of thepreceding examples. The sulfonic acid derivative coatings, however, areless durable.

Immersing a sample of the sulfonic acid-treated fabric in a 5 percentaqueous solution of polyethyleneimine (Tydex 12, Dow Chemical Company)and drying the treated fabric is found to improve coating durabilitywith a slight sacrifice to antisoil properties.

EXAMPLE 20 This example illustrates the treatment of cotton-polyesterfabrics in accordance with the present invention to improve theantisoiling properties thereof.

The general procedure of Example 16 is repeated to apply coatings to afabric of a 65:35 blend of Kodel polyester-cotton which has been treatedwith a formaldehyde derivative to impart a permanent press finish on thefabric. In this example, the coating solution is a 0.5 percent aqueoussolution of the sulfonic acid form of the cellulose xanthate-S-propanesulfonate of Example 2, the sulfonic acid derivative being obtained bycontacting that sulfonate with a strong acid cation exchange resin(Dowex 50H) in the hydrogen ion form. The addon of sulfonated derivativein the resultant dried coated fabric is about 0. l0.2 percent by weightof the fabric.

The resultant coatings of the sulfonic acid derivative on thepolyester-cotton fabric are found to be more durable and to giveimproved antisoiling properties to the treated fabric com parable to thebest coatings of the preceding examples. The

coatings are even soil repellent to the crankcase oil soilant.

EXAMPLE 21 The procedure of Example is repeated except that in thecoating solution used is a 1 percent aqueous solution of thecellulose-S-propane sulfonic acid of Example 6 to provide coatingsrepresenting addons of about 0.25 percent, based on the fabric.

The resultant coatings are found to be durable and impart soil repellentproperties to the treated fabrics comparable to those of the treatedfabrics of Example 16.

EXAMPLE 22 The procedure of Example 21 is repeated except that about 0.1percent DDl diisocyanate, based on the sulfonated derivative, is addedto the sulfonate derivative solution used to coat the polyester-cottonfabric and the solution coated fabrics are heated at about 140 C. tocure and cross-link the sulfonate derivative coating.

The sulfonate coatings in the resultant treated fabrics have excellentdurability and soil repellent properties similar to those of the treatedfabrics of Example 16.

Example 23 The procedure of Example 20 is repeated except that thepermanent press treatment of the starting polyester cotton fabric isomitted, the concentration of the sulfonic acid derivative in thecoating solution is about 0.5 percent, and about 1.5 percent of adihydroxyl dimethylol cyclic ethylene urea (Permafresh 183BT solids) aconventional fabric durable-press finish additive and about 0.075percent zinc nitrate, a catalyst for the durable-press additive, areadded to the sulfonate derivative coating solution. The coating solutionis applied at a liquid pickup by the fabric of about 120 percent and thesolution-coated fabrics are dried at about 105 C. to avoid curing thesensitized resin additive. The dried fabrics then are pressed with aniron at a linen setting to place a crease therein and cure the resin inthe creased fabric. The coating of the resultant creased fabrics thenare tested for durability and soil repellent properties as in Example 16and the durability of the creases therein is noted.

The resultant treated fabrics are found to be durable sulfonatederivative coatings having soil repellent properties slightly reducedfrom those of the treated fabrics of Example 16 and to have durablepress characteristics equivalent to the control fabrics produced usingcoating solutions from which the cellulose sulfonic acid derivative isomitted.

EXAMPLE 24 The procedure of Example 20 is repeated to produce a seriesof treated polyester-cotton fabrics except that, in the preparation ofthe sulfonate derivative coating solutions utilized, the sulfonatederivative employed is the sodium salt of the cellulosexanthate-S-propane sulfonate derivative of Example 2 and each 10, 50,and 100 parts of each polyvinyl alcohol, polyacrylic acid,carboxymethylcellulose, polyvinylpyrrolidone, and spray drieddecausticized cellulose xanthate, separately are added per 100 parts ofthe sulfonic acid derivative.

The resultant treated fabrics produced in each case have coatings ofexcellent durability and soil-repellent properties similar to those ofthe treated fabrics of Example 20.

EXAMPLE 25 The procedure of Example 24 is repeated except that 0.!percent of DB1 diisocyanate is added to each coating solution, and thesolution-coated fabrics are dried to about 140 C. to allow thediisocyanate to cure and cross-link the polymers in the coating.

The resultant treated fabrics, in each case, have excellent durabilityand soil-repellent properties comparable to those of the treated fabricsof Example 20.

EXAMPLE 26 The procedure of Example 20 is repeated except that thecoating solution utilized is 2.8 percent aqueous solution of thesulfonic acid form of the starch-xanthate-S-propane s'ulfonate ofExample 7, the sulfonic acid derivative being obtained by subjecting thesulfonic salt form to a cation exchange treatment as in Example 16. Tothe starch sulfonic acid derivativecontaining coating is added 0.28percent DDI diisocyanate. The solution-coated polyester-cotton fabricsare dried at about 140 C. to cure and cross-link the sulfonated polymersin the coatings. The coatings produced correspond to an addon of about 10-1.5 percent by weight ofthe fabrics.

The resultant treated fabrics show soil-repellent properties which areimproved as compared to control fabrics, but slightly poorer than thoseof the treated fabrics of Example 20.

EXAMPLE 27 This example illustrates the treatment of additional fabricsin accordance with the present invention.

The procedure of Example 17 is repeated to produce an additional seriesof treated fabrics except that a cotton muslin fabric, a wool l 1 oz.flannel fabric, and a nylon fabric, each in turn, is substituted for thepolyester fabric.

The coatings of 05-075 percent addon on the resultant treated fabricsare found to be durable and have improved soil-repellent propertiescomparable to those of the treated polyester fabric of Example 17.

in addition to being useful as antisoiling agents on fabrics and othersoil-receptive substrates, the sulfonated derivatives of the inventionalso find utility in other applications by virtue of the advantageousproperties thereof.

EXAMPLE 28 Solutions of the sulfonated polymeric alcohol derivatives ofthe invention produced as described above typically have relative highviscosities. Aqueous solutions (e.g., 0.1-4 percent of cellulosexanthate-S-propane sulfonates of the invention, for example,surprisingly display viscosities ranging up to times those of similarconcentrations of other polymers such as carboxymethylcellulose ofcorresponding molecular weight. Thus the sulfonated derivatives of theinvention are excellently suited as thickening agents and as suspendingagents in systems containing inorganic and polymeric materials includingfibers, pigments such as titanium dioxide, polymers such as polyacrylicacids, polyvinyl alcohol, polyvinyl acetate and the like.

EXAMPLE 29 An aqueous solution of a polymeric alcohol xanthogenate esteris produced as described in any of the various processes above. Thissolution is used as a binder for pigments (e.g., carbon black andaluminum powder) and dyes such as Anthran Yellow G (C.l. 19020) andOrange 11 (C.l. 15510) in ink formulations. The inks have excellentproperties (nontoxic) and are strongly resistant to rubbing andscratching.

EXAMPLE 30 An aqueous solution of a polymeric alcohol xanthogenate esteris prepared by any of the various methods described above. This solutionis used to apply a sizing coating to a textile such as cotton. The sizedcotton produced has a substantially crisper feel than control pieces.

EXAMPLE 31 Solutions of polymeric alcohol S-xanthogenate esters preparedas described above can be mixed with other polymeric materials toproduce composite articles. Carboxymethylcellulose, amylose, polyvinylalcohol, polyacrylic acid, and the like can be kept in a fine state ofdispersion in such solutions. Such dispersions are effective to producenovel composite articles (e.g., films, fibers, etc.)

EXAMPLE 12 Solutions of polymeric alcohol S-xanthogenate esters preparedas described above can be used as binders which are heat-curable toimprove adhesion between films, fibers, woven fabrics, nonwoven fabricsand sheets, formed of such materials as wood, paper, regeneratedcellulose, cellulose acetate, cotton, wool, nylon, Dacron, oxidizedpolyethylene, and the like.

What is claimed is:

1. A shaped article of a soil-receptive material coated with an adherentcoating comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymericalcohol sulfonic acids containing S-xanthogenate ester substituents ofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts ofsaid polymeric alcohol sulfonic acids.

2. A coated article according to claim 1 wherein said shaped article isa filament, fiber, film, or a nonwoven or woven fabric.

3. A coated article according to claim 2 wherein said shaped article isa cotton-containing fabric.

4. A coated article according to claim 2 wherein said shaped article isa polyester-containing fabric.

5. A coated article according to claim 2 wherein said shaped article isa wool fabric.

6. A shaped article according to claim 1 wherein said sulfonate compoundis a polymeric alcohol sulfonate derivative having a degree ofsubstitution with regard to said S- xanthogenate ester substituents inthe range of from about 0.001 to about 1.0 and having a molecular weightin the range of from about 1,000 to about 5,000.000.

7. A shaped article according to claim 6 wherein said sulfonate compoundis a polymeric alcohol sulfonate derivative wherein X is sulfur.

8. A shaped article according to claim 7 wherein said sulfonate compoundis a polymeric alcohol sulfonate derivative wherein R is CH CH CH Ashaped article according to claim 7 wherein said sulfonate compound is apolymeric alcohol sulfonate derivative wherein said polymeric alcohol isa polysaccharide.

10. A shaped article according to claim 7 wherein said sulfonatecompound is a sulfonated cellulose derivative.

11. A shaped article according to claim 7 wherein said sulfonatecompound is a sulfonated starch derivative.

12. A shaped article according to claim 7 wherein said sulfonatecompound is a sulfonated polyvinyl alcohol derivative.

13. A shaped article according to claim 7 wherein said sulfonatecompound is a sulfonated chitin or chitosan derivative.

14. A shaped article according to claim 7 wherein said sulfonatecompound is a film-forming polymeric alcohol sulfonate derivative.

15. A shaped article according to claim '7 wherein said sulfonatecompound is a water-soluble polymeric alcohol sulfonic acid.

16. A shaped article according to claim 7 wherein said sulfonatecompound is a water-soluble polymeric alcohol sulfonate salt.

17. A shaped article according to claim 7 wherein said sulfonatecompound is a water-insoluble polymeric alcohol sulfonate derivative.

18. A shaped article according to claim 17 wherein said sulfonatecompound is a water-insoluble polymeric alcohol sulfonate derivativecomprising a multivalent metal salt of said polymeric alcohol sulfonicacids.

19. A shaped article according to claim 17 wherein said sulfonatecompound is a water-insoluble polymeric alcohol sulfonate derivativecomprising a cross-linked derivative of said polymeric alcohol sulfonicacids and sulfonate acid salts.

20. A shaped article according to claim 6 wherein said sulfonatecompound is a water-soluble polymeric alcohol sulfonic acid having amolecular weight of at least about 25,000 and wherein X is sulfur.

21. A shaped article according to claim 20 wherein said sulfonatecompound is a water-soluble cellulose xanthate-S- propane sulfonic acid.

22. A shaped article according to claim 20 wherein said sulfonatecompound is a water-soluble starch xanthate-S- propane sulfonic acid.

23. A shaped article according to claim 20 wherein said sulfonatecompound is a water-soluble polyvinyl alcohol xanthate-S-propanesulfonic acid.

24. A shaped article according to claim 6 wherein said sulfonatecompound is a water-soluble polymeric alcohol sulfonate salt having amolecular weight of at least about 25,000 and wherein X is sulfur.

25. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble cellulose xanthate-S- propane sulfonatesalt.

26. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble starch xanthate-S- propane sulfonate salt.

27. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble polyvinyl alcohol xanthate-S-propanesulfonate salt.

28. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble chitin chitosan xanthate- S-propanesulfonate salt.

29. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble polymeric alcohol alkali metal sulfonatesalt.

30. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble cellulose xanthate-S- propane-alkali metalsulfonate.

31. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble starch xanthate-S- propane-alkali metalsulfonate.

32. A shaped article according to claim 24 wherein said sulfonatecompound is a water-soluble polyvinyl alcohol xanthate-S-propane-alkalimetal sulfonate.

33. A method for producing a shaped article having improved antisoilingproperties comprising coating the surface of said shaped article with acomposition comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymericalcohol sulfonic acids containing S-xanthogenate ester substituentsofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids, wherein said coating isapplied as a solution or dispersion of said sulfonated compound in aliquid vehicle to the surface of said shaped article and said liquidvehicle subsequently is removed from the so applied solution ordispersion to form a dried surface deposit on said shaped article.

34. A method for producing a shaped article having improved anti-soilingproperties comprising coating the surface of said shaped article with acomposition comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymericalcohol sulfonic acids containing S-xanthogenate ester substituentsofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids, wherein said sulfonatedcompounds coating is produced in situ on the surface on said shapedarticle.

357 A method for producing a shaped article having improved antisoilingproperties comprising coating the surface of said shaped article with acomposition comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymerica]- cohol sulfonic acids containing S-xanthogenate ester substituents ofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said li'near alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids, wherein said coating isformed by heating a coating of said sulfonated compound on the surfaceof said shaped article to a tempera ture in excess of 100 C.

36. A method for producing a shaped article having improved antisoilingproperties comprising coating the surface of said shaped article with acomposition comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymericalcohol sulfonic acids containing S-xanthogenate ester substituentsofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids, wherein said coating isapplied by coating the surface of said shaped article with a solution ofsaid sulfonated compound and reacting the same with a multivaient inetalcompound.

377 A method for producing a shaped article having improved antisoilingproperties comprising coating the surface of said shaped article with acomposition comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymericalcohol sulfonic acids containing S-xanthogenate ester substituents ofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids, wherein said coatingmaterial is formed by coating the surface of said shaped article with asolution of said sulfonated compound and reacting the same with across-linking agent,

* a a at

2. A coated article according to claim 1 wherein said shaped article isa filament, fiber, film, or a nonwoven or woven fabric.
 3. A coatedarticle according to claim 2 wherein said shaped article is acotton-containing fabric.
 4. A coated article according to claim 2wherein said shaped article is a polyester-containing fabric.
 5. Acoated article according to claim 2 wherein said shaped article is awool fabric.
 6. A shaped article according to claim 1 wherein saidsulfonate compound is a polymeric alcohol sulfonate derivative having adegree of substitution with regard to said S-xanthogenate estersubstituents in the range of from about 0.001 to about 1.0 and having amolecular weight in the range of from about 1,000 to about 5,000,000. 7.A shaped article according to claim 6 wherein said sulfonate compound isa polymeric alcohol sulfonate derivative wherein X is sulfur.
 8. Ashaped article according to claim 7 wherein said sulfonate compound is apolymeric alcohol sulfonate derivative wherein -R-is -CH2CH2CH2-.
 9. Ashaped article according to claim 7 wherein said sulfonate compound is apolymeric alcohol sulfonate derivative wherein said polymeric alcohol isa polysaccharide.
 10. A shaped article according to claim 7 wherein saidsulfonate compound is a sulfonated cellulose derivative.
 11. A shapedarticle according to claim 7 wherein said sulfonate compound is asulfonated starch derivative.
 12. A shaped article according to claim 7wherein said sulfonate compound is a sulfonated polyvinyl alcoholderivative.
 13. A shaped article according to claim 7 wherein saidsulfonate compound is a sulfonated chitin or chitosan derivative.
 14. Ashaped article according to claim 7 wherein said sulfonate compound is afilm-forming polymeric alcohol sulfonate derivative.
 15. A shapedarticle according to claim 7 wherein said sulfonate compound is awater-soluble polymeric alcohol sulfonic acid.
 16. A shaped articleaccording to claim 7 wherein said sulfonate compound is a water-solublepolymeric alcohol sulfonate salt.
 17. A shaped article according toclaim 7 wherein said sulfonate compound is a water-insoluble polymericalcohol sulfonate derivative.
 18. A shaped article according to claim 17wherein said sulfonate compound is a water-insoluble polymeric alcoholsulfonate derivative comprising a multivalent metal salt of saidpolymeric alcohol sulfonic acids.
 19. A shaped article according toclaim 17 wherein said sulfonate compound is a water-insoluble polymericalcohol sulfonate derivative comprising a cross-linked derivative ofsaid polymeric alcohol sulfonic acids and sulfonate acid salts.
 20. Ashaped article according to claim 6 wherein said sulfonate compound is awater-soluble polymeric alcohol sulfonic acid having a molecular weightof at least about 25,000 and wherein X is sulfur.
 21. A shaped articleaccording to claim 20 wherein said sulfonate compound is a water-solublecellulose xanthate-S-propane sulfonic acid.
 22. A shaped articleaccording to claim 20 wherein said sulfonate compound is a water-solublestarch xanthate-S-propane sulfonic acid.
 23. A shaped article accordingto claim 20 wherein said sulfonate compound is a water-soluble polyvinylalcohol xanthate-S-propane sulfonic acid.
 24. A shaped article accordingto claim 6 wherein said sulfonate compound is a water-soluble polymericalcohol sulfonate salt having a molecular weight of at least about25,000 and wherein X is sulfur.
 25. A shaped article according to claim24 wherein said sulfonate compound is a water-soluble cellulosexanthate-S-propane sulfonate salt.
 26. A shaped article according toclaim 24 wherein said sulfonate compound is a water-soluble starchxanthate-S-propane sulfonate salt.
 27. A shaped article according toclaim 24 wherein said sulfonate compound is a water-soluble polyvinylalcohol xanthate-S-propane sulfonate salt.
 28. A shaped articleaccording to claim 24 wherein said sulfonate compound is a water-solublechitin chitosan xanthate-S-propane sulfonate salt.
 29. A shaped articleaccording to claim 24 wherein said sulfonate compound is a water-solublepolymeric alcohol alkali metal sulfonate salt.
 30. A shaped articleaccording to claim 24 wherein said sulfonate compound is a water-solublecellulose xanthate-S-propane-alkali metal sulfonate.
 31. A shapedarticle according to claim 24 wherein said sulfonate compound is awater-soluble starch xanthate-S-propane-alkali metal sulfonate.
 32. Ashaped article according to claim 24 wherein said sulfonate compound isa water-soluble polyvinyl alcohol xanthate-S-propane-alkali metalsulfonate.
 33. A method for producing a shaped article having improvedantisoiling properties comprising coating the surface of said shapedarticle with a composition comprising a sulfonated compound consistingof a polymeric alcohol derivative selected from the group consisting of(a) polymeric alcohol sulfonic acids containing S-xanthogenate estersubstituents of the general formula wherein X is oxygen or sulfur and Ris a divalent hydrocarbon radical selected from the group consisting oflinear alkylene radicals of three to six carbon atoms and said linearalkylene radicals containing lower alkyl substituents, and (b) total andpartial salts of said polymeric alcohol sulfonic acids, wherein saidcoating is applied as a solution or dispersion of said sulfonatedcompound in a liquid vehicle to the surface of said shaped article andsaid liquid vehicle subsequently is removed from the so applied solutionor dispersion to form a dried surface deposit on said shaped article.34. A method for producing a shaped article having improved anti-soilingproperties comprising coating the surface of said shaped article with acomposition comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymericalcohol sulfonic acids containing S-xaNthogenate ester substituents ofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids, wherein said sulfonatedcompounds coating is produced in situ on the surface on said shapedarticle.
 35. A method for producing a shaped article having improvedantisoiling properties comprising coating the surface of said shapedarticle with a composition comprising a sulfonated compound consistingof a polymeric alcohol derivative selected from the group consisting of(a) polymeric alcohol sulfonic acids containing S-xanthogenate estersubstituents of the general formula wherein X is oxygen or sulfur and Ris a divalent hydrocarbon radical selected from the group consisting oflinear alkylene radicals of three to six carbon atoms and said linearalkylene radicals containing lower alkyl substituents, and (b) total andpartial salts of said polymeric alcohol sulfonic acids, wherein saidcoating is formed by heating a coating of said sulfonated compound onthe surface of said shaped article to a temperature in excess of 100* C.36. A method for producing a shaped article having improved antisoilingproperties comprising coating the surface of said shaped article with acomposition comprising a sulfonated compound consisting of a polymericalcohol derivative selected from the group consisting of (a) polymericalcohol sulfonic acids containing S-xanthogenate ester substituents ofthe general formula wherein X is oxygen or sulfur and R is a divalenthydrocarbon radical selected from the group consisting of linearalkylene radicals of three to six carbon atoms and said linear alkyleneradicals containing lower alkyl substituents, and (b) total and partialsalts of said polymeric alcohol sulfonic acids, wherein said coating isapplied by coating the surface of said shaped article with a solution ofsaid sulfonated compound and reacting the same with a multivalent metalcompound.
 37. A method for producing a shaped article having improvedantisoiling properties comprising coating the surface of said shapedarticle with a composition comprising a sulfonated compound consistingof a polymeric alcohol derivative selected from the group consisting of(a) polymeric alcohol sulfonic acids containing S-xanthogenate estersubstituents of the general formula wherein X is oxygen or sulfur and Ris a divalent hydrocarbon radical selected from the group consisting oflinear alkylene radicals of three to six carbon atoms and said linearalkylene radicals containing lower alkyl substituents, and (b) total andpartial salts of said polymeric alcohol sulfonic acids, wherein saidcoating material is formed by coating the surface of said shaped articlewith a solution of said sulfonated compound and reacting the same with across-linking agent.